JP2007503516A - Composition comprising a dispersant and microcapsules containing an active substance and a stabilizer - Google Patents

Abstract

  A composition for providing controlled release of an active agent includes a dispersant and microcapsules containing the active agent and a stabilizer. The composition contains a relatively low concentration of dispersant and / or microcapsules to avoid adversely affecting the surface treated with the composition. The active substance is preferably a perfume, and the composition provides a controlled release scent as well as controlling malodor when the composition further comprises an optional odor control agent. Stabilizers improve the stability of the microcapsules. A method for providing controlled release of an active agent on a surface includes contacting the surface with a composition containing a dispersant and microcapsules containing the active agent and stabilizer.

Description

  The present invention relates to a composition that can be applied to surfaces, including carpets, fabrics and other household surfaces, to provide controlled release of the scent of an active substance, preferably a perfume, to the environment surrounding the surface.

  Fabric refresher products have become popular in today's consumer market. Such products typically include a liquid composition that is sprayed onto a surface, such as a fabric, to reduce or remove malodor from the surface. Some of these products can also provide a pleasant scent by incorporating perfume into the composition. However, such products typically cannot provide controlled release of active substances such as perfume scents.

  Other products only give a pleasant fragrance and do not act to reduce or eliminate odors. Such products instead use the strong scent of perfume to mask the odor by giving it a stronger scent. JP-03-173,565 ("JP'565") discloses an encased fragrance spray composition in which the fragrance is encapsulated in microcapsules. The spray composition is preferably an aerosol composition utilizing a propellant. Perfume-encapsulating microcapsules adhere to clothing, carpets, ties, and the like, and fragrances are gradually released or released by pressure such as friction. The JP'565 spray composition contains a relatively high concentration of microcapsules and / or binders that provide the preferred fragrance but can adversely affect the surface being treated.

  JP-11-246383 ("JP'383") also discloses a composition made from a slurry of microcapsules containing an essential oil mixed with an aqueous binder. The composition can be applied to fibers such as bed sheets, for example, when a person is sleeping, the fragrance can be released from the microcapsules. However, like the JP'565 spray composition, the JP'383 composition provides a preferred fragrance, but a relatively high concentration of microcapsules and / or binders that can adversely affect the surface being treated. Contains.

  U.S. Pat. No. 4,520,142 ("US'142") discloses a liquid encapsulated in a microcapsule, such as a fragrance, applied to a substrate from an aerosol applicator. The aerosol composition of US'142 contains a microcapsule containing a liquid, a polymeric binder, a solvent for the polymeric binder, and an aerosol propellant. However, while the US '142 aerosol composition provides controlled release of liquid substances, this composition contains relatively high concentrations of microcapsules and / or binders that can adversely affect the surface being treated. Contains.

  Microcapsules are used in many types of products, but over time the stability of microcapsules can become a problem. In solutions containing water and / or volatile substances, the microcapsules can collapse or rupture over time, causing the active substance in the microcapsules to be released prematurely. These losses often reduce the effectiveness of the product, necessitating the use of increased product to achieve satisfactory results. Due to inadvertent release of the active agent from the microcapsules, the active agent is not effectively delivered.

  Accordingly, there is a need to provide a composition that can provide controlled release of the scent of an active substance, preferably a perfume, to the environment surrounding the surface without adversely affecting the treated surface. There is also a need to provide compositions that can provide controlled release of the active agent and that can kill microorganisms on the surface treated with the composition. There is a further need to form compositions containing microcapsules that are stable over time. The present invention addresses these previously unmet needs.

  The present invention comprises a microcapsule containing a dispersant, an active substance, a stabilizer and / or any odor control agent (which may be referred to herein as “encapsulated odor control agent”), an aqueous The present invention relates to a composition comprising a carrier (non-aerosol and aerosol). Without being bound by theory, it is believed that the stabilizer stabilizes the microcapsule by preventing water and / or volatile materials from entering through cracks and defects within the microcapsule. The composition preferably contains a relatively low concentration of dispersant and / or microcapsules to avoid adversely affecting the treated surface. The composition can be applied to a surface, such as a fabric, to provide controlled release of the active agent on the surface or the environment surrounding the surface. The active substance is preferably a fragrance. The stabilizer is preferably isopropyl myristate. The composition can provide a controlled release scent.

  The invention further relates to an antimicrobial composition comprising a dispersant, microcapsules containing an active substance, an antimicrobial active substance and a stabilizer, and an aqueous carrier.

The invention further relates to methods of using these compositions comprising the step of contacting the surface with the composition.
The invention further relates to a method for producing a composition comprising a dispersant and microcapsules containing an active substance and a stabilizer.
The invention further relates to the use of a composition comprising a dispersant and microcapsules containing the active substance and stabilizer for providing a controlled release of the active substance on and / or surrounding the surface. .

  All references cited in this specification are incorporated herein by reference in their relevant parts, and any citation of any reference is construed as an admission that it is prior art relevant to the present invention. Should not.

  It is to be understood that any maximum numerical limitation set forth throughout this specification includes any numerical limitation that is less than that, as if such lower numerical limitations were expressly set forth herein. is there. Any minimum numerical limitation set forth throughout this specification will include any numerical limitation higher than that, as if such large numerical limitation was expressly set forth herein. All numerical ranges given throughout this specification are intended to express any numerical range narrower than that falling within such broader numerical ranges, and all such narrower numerical ranges are expressly set forth herein. Include as if.

  Unless otherwise specified, all parts, ratios, and percentages in the specification, examples, and claims are based on weight and all numerical limitations are to the extent permitted by the art. Used with precision.

  The composition of the present invention comprises a microcapsule containing an active substance, a stabilizer, and / or any odor control agent (which may be referred to herein as “encapsulated odor control agent”), Contains a dispersant, as well as an aqueous carrier. The composition can also include a wide variety of additional optional ingredients such as odor control agents, solvents, aerosol propellants, surfactants, free fragrances, antimicrobial actives / preservatives, wrinkle control agents, and the like. The compositions herein include both non-aerosol and aerosol compositions. The composition can be used to provide controlled release of the active agent and / or any odor control agent. When the active substance is a perfume, the composition provides a controlled release scent.

  It should be understood that the active agent and stabilizer need not be fully encapsulated (ie, in some embodiments, it may be partially encapsulated). The same is true for microcapsules containing encapsulated odor control agents.

  There are a non-limiting number of embodiments of the compositions described herein. These embodiments include, but are not limited to, embodiments in which at least some of the same microcapsules contain active substances, stabilizers and optional odor control agents therein. In other embodiments, the composition may comprise a group of microcapsules containing active substances and stabilizers and different microcapsules containing optional odor control agents and stabilizers. The composition may comprise microcapsules with different types of shells or coating materials. In addition, in some embodiments, the encapsulated odor control agent and the odor control agent outside the microcapsule may be the same odor control agent. In other embodiments, they may be different odor control agents.

  The composition preferably comprises relatively low concentrations of microcapsules and / or dispersants to avoid adversely affecting the surface treated with the composition. For example, if the composition contains too much microcapsules and / or dispersant, the potential of this composition is to leave an undesirable visible residue on the surface treated with the composition Problems can occur. Furthermore, if the surface is a fabric and the composition has too much dispersant, the composition can cause the fabric to feel undesirably stiff and / or lose the softness of the hand.

(Micro capsule)
The composition comprises microcapsules containing an active substance, a stabilizer, and an optional odor control agent. Microcapsules provide controlled release of active substances, stabilizers and optional odor control agents contained within the microcapsules. The microcapsules in the composition of the present invention are burstable capsules containing active substances, stabilizers and / or optional odor control agents therein, or active substances, stabilizers and / or encapsulated therein. Capsules can control the penetration of any odor control agent. The burst strength of the microcapsules can withstand handling and spraying without rupturing, but should be within a range that breaks when a frictional force is applied to the entire surface treated with the composition.

  Microcapsule shells can be made from a wide variety of materials. Such materials are typically polymeric and are designed not to be solubilized in the chemical matrix of the composition. Non-limiting examples of materials suitable for producing the microcapsule shells herein include urea formaldehydes, melamine formaldehydes, phenol formaldehydes, gelatin, poly (vinyl alcohol), poly (vinyl pyrrolidone), poly Acrylates, polyamides, polyurethanes, polymethacrylates, polyepoxides, cellulose acetate, cellulose nitrate, cellulose acetate butyrate, ethyl cellulose polyester, polychlorotrifluoroethylene (eg KEL-F), ethyl acetate // vinyl acetate, saran ( saran), polystyrene, zein, paraffin wax, animal wax, vegetable wax, microcrystalline wax, polyethylene wax and the like. Preferred microcapsule shell materials include poly (oxymethylene urea), poly (oxymethylene melamine), gelatin, polyurethane, and mixtures thereof. Other suitable microcapsule shell materials include, for example, U.S. Pat. Nos. 2,800,458; 3,159,585; 3,516,846; 3,533,958; No. 3,697,437; No. 3,888,689; No. 3,996,156; No. 3,965,033; No. 4,010,038; No. 4,016,098 No. 4,087,376; No. 5,591,146; British Patents 2,006,709 and 2,062,570; and Benita, Simon (ed.), Micro Encapsulation: disclosed in MICROENCAPSULATION: METHODS AND INDUSTRIAL APPLICATIONS (Marcel Dekker, Inc., 1996).

  The size of the microcapsules can be important in terms of the usefulness of the microcapsules according to the practice of the present invention. Generally, the microcapsules have an average diameter of about 0.001 to about 1,000 microns, preferably about 1 to about 500 microns, more preferably about 10 to about 100 microns, and even more preferably about 20 to about 85 microns. . These dimensions can play an important role in the ability to control capsule application in the practice of the invention. The widest range of capsule sizes under any conditions is from about 0.001 to about 1,000 microns, and the more easily sprayed size limit is from about 20 to about 85 microns.

  In general, the composition can include microcapsules in a wide variety of concentrations. The microcapsules are typically from about 0.001% to about 99.9%, preferably from about 0.005% to about 50%, more preferably from about 0.01% by weight of the composition. It is included in the composition at a concentration of about 20% by weight. When the composition is an aqueous liquid composition (especially a non-aerosol composition) that is sprayed onto a surface such as a fabric, the composition is preferably less than about 1% by weight of the composition, preferably about 0.9% by weight. Less than about 0.5%, more preferably less than about 0.5%, even more preferably less than about 0.2% by weight of microcapsules. If the concentration of microcapsules is too high, the composition may leave a visible residue on the surface to be treated. In addition, if the surface is a fabric and the concentration of microcapsules is too high, the appearance of the fabric may be changed. In addition, if the active substance is a perfume and the concentration of the microcapsules is too high, the spraying power tends to rupture some of the microcapsules, so there is a “burst” of the initial perfume when the product is sprayed onto the surface. May be uncomfortable for consumers.

  Various methods known in the art can be used to produce the microcapsules herein. Examples of methods for producing microcapsules include U.S. Pat. Nos. 2,800,458; 3,159,585; 3,516,846; 3,516,941; No. 3,697,437; No. 3,778,383; No. 3,888,689; No. 3,965,033; No. 3,996,156 No. 4,010,038; No. 4,016,098; No. 4,087,376; No. 4,089,802; No. 4,100,103; No. 251,386; No. 4,269,729; No. 4,303,548; No. 4,460,722; and No. 4,610,927; British Patent No. 1,156,725; 1,483,542; 2,041,319 and 2,048,206, In Benita, Simon (ed.), Microencapsulation: MICROENCAPSULATION: METHODS AND INDUSTRIAL APPLICATIONS (Marcel Dekker, Inc., 1996). .

(Active substance)
The active substance can be a wide variety of substances that are desired to be delivered in a controlled release manner to the surface treated with the composition or to the environment surrounding the surface. Non-limiting examples of active substances include fragrances, flavorings, fungicides, brighteners, antistatic agents, wrinkle suppressants, softeners, hard surface cleaners, skin and / or hair conditioning agents, antimicrobial active substances, UV protection agents, insect repellents, animal / pest repellents, flame retardants and the like.

  In a preferred embodiment, the active substance is a perfume, where the microcapsules containing the perfume provide a controlled release scent to the surface to be treated or to the environment surrounding that surface. In this case, the perfume can be composed of a number of perfume raw materials known in the art, such as essential oils, plant extracts, synthetic perfume materials and the like.

  Generally, the active agent is present in the microcapsule at a concentration of about 1% to about 99%, preferably about 10% to about 95%, more preferably about 30% to about 90% by weight of the total microcapsule. Contained in The total weight of the microcapsule includes the shell weight of the microcapsule and the weight of the substance in the microcapsule. Encapsulated odor control agents, if present, may be contained in the microcapsules in the same concentration range. Of course, when both the active substance and the odor control agent are contained in the same microcapsule, the total proportion of these components never exceeds 100%.

  Microcapsules containing active substances, preferably perfumes, suitable for use in the present compositions are described, for example, in US Pat. Nos. 3,888,689; 4,520,142; No. 061; and US Pat. No. 5,591,146.

(Stabilizer)
Stabilizers can be a wide variety of materials that provide additional stability to the microcapsules. Ideal stabilizers have little or no odor in the amount they are used. Examples of stabilizers that can be used in the present invention include isopropyl myristate, diethyl phthalate, triethyl citrate, mineral oil, silicone oil, diethyl propyl acetate, benzyl phenyl acetate (acteate), citronellyl phenyl acetate, benzyl isoeugenol, diphenyl Oxide, γ-dodecalactone, dibutyl phthalate, methyl myristate, ethyl myristate, ethyl palmitate, benzyl salicylate, benzyl benzoate, pheyl ethyl phenylacetate, geranyl phenylacetate (aceate), benzyl cinnamate, Ethylene brush rate, ambretone, galaxolide, tonalide, exaltolide, habanolide, isoamyl laurate, cedryl acetate, hexyl cinnamon alde De, patchouli alcohol, .delta. Guaien, .delta. cadinene, C ₁₀ or higher alcohols, Dowanol (Dowanol) (registered trademark), dipropylene myristate and tripropylene myristate, Isopar (R), orange terpenes and their A mixture of, but not limited to. Particularly preferred is isopropyl myristate.

  Generally, the stabilizer is contained in the microcapsule at about 1% to about 99%, preferably about 10% to about 95%, more preferably about 30% to about 70% by weight of the total microcapsule. Is done. The total weight of the microcapsule includes the shell weight of the microcapsule and the weight of the substance in the microcapsule.

(Stability of microcapsules)
Stabilizers are added with the active substance to increase the stability of the microcapsules. By adding a stabilizer to the microcapsule, the microcapsule retains more active substance over time. It has been found that the stability of microcapsules can be measured as a function of the Kobat number of the contents of the microcapsules. The Kobat number of the contents of the microcapsules is determined by weighing the sample using a chemical balance and placing it in a 100 mL volumetric flask and diluting to volume with methanol. The sample is then placed in a gas chromatograph vial and a 6890 gas chromatograph using a DB-5 ((5% phenyl) -methylpolysiloxane coating) (inner diameter 0.25 mm, film thickness 1 μm, length 30 m) column. The graph is implemented. The sample is subjected to the following conditions:

Area ratio records are generated using flame ionization detector (FID) data, and the average weighted Kobat number is calculated on the contents of the microcapsules. The Kobat number is first calculated for each of the active and stabilizer components using the following equation:
Kobatto Index _{= (((logRT x -logRT y} ) / (logRT z -logRT y)) × 100) + (N y × 100)
RT _x = retention time of the relevant peak RT _y = retention time of the hydrocarbon before the relevant peak RT _z = retention time of the hydrocarbon after the relevant peak N _y = number of hydrocarbon carbons before the relevant peak

  After calculating the number of Kobat for each of the individual active and stabilizer components, the number of weight Kobat is calculated by multiplying the area percentage of the component by the calculated number of Kobat. Next, the number of weight Kobat of each component is added to obtain the weight average Kobat number of each of the active substance and the stabilizer. Further description of the procedure for determining the number of Kobat can be found in “Chromatographic Retention Indices-An Aid to Identification of Organic Compounds”, Vera Pacakova and Ladisley Feltre ( Ladislay Feltl), Ellis Horward Limited, New York, 199 pages.

  In general, the combination of stabilizer and active substance in the microcapsule has a weight average Kobat number greater than about 1325, preferably greater than about 1375, more preferably greater than about 1400, and even more preferably greater than about 1450. .

(Dispersant)
The composition further comprises a dispersant. The dispersant may be important for suspending the microcapsules in the composition so as to prevent the microcapsules from leaving the solution. Thus, the dispersant may be important in achieving a composition that is stable.

  If the composition is designed to be sprayed from a spray dispenser, select a concentration and type of dispersant that provides sufficient suspension in the microcapsule particles, but at the same time can be easily sprayed as a fine mist. It can be important. Some dispersants are capable of suspending the particles, but result in a composition having a viscosity so high that it cannot be easily sprayed as a fine mist.

In this regard, the concentration and type of dispersant is preferably selected to provide non-Newtonian viscosity characteristics. Accordingly, the malodor control composition obtained preferably has a viscosity difference of at least about 0.0001 Pa.s at a shear rate of 1 sec ^-1 and 10 sec ^-1 . s, (0.1 centipoise), preferably at least about 0.0005 Pa.s. s (0.5 centipoise), more preferably at least about 0.001 Pa.s. s (1 centipoise). In this regard, the compositions herein are preferably shear thinning. The resulting composition can suitably suspend particles (eg, microcapsules) therein, but can be easily sprayed from a spray dispenser at the same time.

  Preferred dispersants herein are shear thinning compositions that have a weak gel-forming matrix in which polymeric or non-polymeric components interact with each other to form hydrogen and / or hydrophobic bonds I will provide a. Some functional groups on the molecule have an electrostatic repulsion that can prevent solidification of the particles in the composition. The weakly formed gel matrix obtained from the preferred dispersants herein can suspend micron-sized particles, such as microcapsules, in the composition matrix.

  When present, the dispersant is typically about 0.001% to about 10%, preferably about 0.005% to about 5%, more preferably about 0.01% by weight of the composition. % To about 1% by weight. When it is desirable to keep the viscosity of the composition relatively low, for example when the composition is sprayed onto a surface (eg, a fabric) via a spray dispenser, the dispersant is preferably about 1% by weight of the composition Less than, more preferably less than about 0.9% by weight, even more preferably less than about 0.8% by weight. If the concentration of dispersant is too high, the composition may leave a visible residue on the treated surface. If the composition is sprayed onto the fabric and the dispersant concentration is too high, the composition may change the feel or softness of the fabric to an undesirable one.

  Dispersants herein include pectin, alginate, arabinogalactan, carrageenan, gellan gum, xanthum gum, guar gum, acrylate / acrylic polymers, water swellable clays, fumed silicas, acrylate / amino acrylate copolymers And materials such as mixtures thereof. Preferred dispersants herein include those selected from the group consisting of acrylate / acrylic polymers, gellan gum, fumed silicas, acrylate / aminoacrylate copolymers, water-swellable clays, and mixtures thereof.

  Acrylate / acrylic polymers include acrylic emulsion terpolymers. This type of dispersant is typically alkali activated. Suitable alkali activated acrylate / acrylic polymers are described in detail in US Pat. Nos. 5,990,233 and 5,840,789. Such alkali activated acrylate / acrylic polymer dispersants are available from Alco Chemical under the trade name ALCOGUM® SL series.

  Gellan gum is a heteropolysaccharide prepared by fermentation of Pseudomonaselodea ATCC 31461. Gellan gum is available in various forms including KELCOGEL (R), Kelcogel (R) LT100, Kelcogel (R) AFT, Kelcogel (R) AF, Kelcogel (R) PC and Kelcogel (R) F It is available from CP Kelco US, Inc. by name. Methods for preparing gellan gum are described in US Pat. No. 4,326,052 (Kang et al., Issued April 20, 1982); US Pat. No. 4,326,053 (Kang et al., April 1982). U.S. Pat. No. 4,377,636 (Kang et al., Issued March 22, 1983); and U.S. Pat. No. 4,385,123 (Kang et al., Issued May 24, 1983). Has been.

Fumigated silicas are colloidal forms of silica produced by the combustion of silicon tetrachloride in a hydrogen-oxygen furnace. Fumigated silicas are known by the chemical name silicon dioxide. Fumigated silicas suitable for the present composition are available from Degussa AG under the trade name AEROSIL®. A preferred fumed silica is AEROSIL® 200 (available from Degussa AG), which is a hydrophilic fumed silica having a specific surface area of about 200 m ² / g.

  Acrylate / aminoacrylate copolymers are typically aqueous dispersants of rheology modifiers of amine functional acrylic polymers. This type of dispersant is typically acid activated compared to the acrylate / acrylic polymer dispersions described hereinabove which are typically alkali activated. Acrylate / aminoacrylate copolymers are available from Alco Chemical under the trade name ALCOGUM® L-500 series. Preferred acrylate / aminoacrylate copolymers are ALCOGUM® L-511 and Alcogum® L-520, which are amine functional acrylic polymers available from Alco Chemical. It is an aqueous dispersant.

  Water swellable clays include hectorites and synthetic layered silicates. Synthetic layered silicates are available from Southern Clay Products, Inc. under the trade name LAPONITE®. These synthetic layered silicates are layered hydrous magnesium silicates, where suitable monovalent ions such as lithium, sodium, potassium and / or magnesium ions partially substituted by vacancies are oxygen and Octahedrally coordinated to hydroxyl ions, some of which may be substituted with fluorine ions to form a central octahedral sheet, which is a silicon ion tetrahedrally coordinated to oxygen Between the two tetrahedron sheets. Preferred synthetic layered silicates include LAPONITE® RD and Laponite® RDS available from Southern Clay Products, Inc. Hectorites are available from Rheox, Inc. under the trade name BENTONE®. These hectorites are prepared by reacting bentonite in a cation exchange system using an amine. Preferred hectorites include BENTONE® LT and BENTONE® AD available from Rheox, Inc.

(Aqueous carrier)
The aqueous carrier of the present invention contains water. The water used can be distilled, deionized or tap water. Water not only acts as a liquid carrier for the microcapsules, but when the surface is treated, the odor control agent and any undesirable molecules on the surface, such as malodorous molecules on inanimate surfaces such as fabrics. It also promotes the reaction. It has been found that when the odor-contaminated surface is treated with an aqueous solution, the intensity of undesirable malodorous molecules produced by some polar, low molecular weight organic amines, acids, and mercaptans is reduced. Water is believed to solubilize these polar, low molecular weight organic molecules and lower the vapor pressure, thereby reducing its odor intensity.

  The concentration of the aqueous carrier in the composition can vary depending on the use of the composition. In general, the concentration of the aqueous carrier in the composition can be from about 0.1% to about 99.9%. In compositions designed to be sprayed from a manually or non-manually operated spray dispenser, the concentration of the aqueous carrier is preferably high, for example at least about 80%, preferably at least about 85% by weight of the composition. More preferably at least about 90% by weight, even more preferably at least about 95% by weight.

(Optional component)
The composition can further include a wide variety of optional ingredients such as odor control agents, solvents, aerosol propellants, surfactants, free perfumes, preservatives / antibacterial actives, wrinkle control agents, and the like.

(Odor control agent)
The composition is optionally but preferably about 0.001% to about 99.99% by weight of the malodor control composition, preferably about 0.002% to about 99.9%, more preferably Further comprises one or more odor control agents at a concentration of from about 0.005% to about 99%. When the composition is an aqueous liquid composition (especially a non-aerosol composition) that is sprayed onto a surface such as a fabric, the composition is preferably less than about 20%, preferably about 10% by weight of the composition. Less, more preferably less than about 5% by weight of odor control agent. The odor control agent helps to reduce or eliminate malodor from the surface or object being treated with the composition. The odor suppressor is preferably selected from the group consisting of uncomplexed cyclodextrins; odor blockers; reactive aldehydes; flavanoids; zeolites; activated carbon; and mixtures thereof. The compositions herein comprising an odor control agent can be used in a method of reducing or eliminating malodors from surfaces treated with the composition.

(Uncomplexed cyclodextrin)
As used herein, the term “uncomplexed cyclodextrin” includes unsubstituted cyclodextrins containing 6-12 glucose units, in particular α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin. Mention may be made of known cyclodextrins in uncomplexed form, such as dextrin and / or derivatives thereof and / or mixtures thereof. α-cyclodextrin consists of 6 glucose units arranged in a donut-shaped ring, β-cyclodextrin consists of 7 glucose units, and γ-cyclodextrin consists of 8 glucose units . The unique binding and structure of the glucose unit gives the cyclodextrin a rigid, conical molecular structure with a characteristic volume of cavities inside. The “lining” of each inner cavity is formed by hydrogen atoms and oxygen atoms bridging the glycosides, so this surface is quite hydrophobic. The unique shape and physicochemical properties of the cavity allow the cyclodextrin molecule to absorb (with it form an inclusion complex) an organic molecule or part of an organic molecule that can fit into the cavity. . Numerous odorous molecules can fit into the cavity, including numerous malodorous and perfume molecules. Thus, cyclodextrins, especially mixtures of cyclodextrins with different sized cavities, suppress the odor caused by the broad spectrum of fragrant organic substances that may or may not contain reactive functional groups. Can be used. Complexation of cyclodextrin with odorous molecules occurs rapidly in the presence of water. However, the degree of complex formation also depends on the polarity of the absorbed molecules. In aqueous solutions, highly hydrophilic molecules (those that are very water soluble) are only partially absorbed, if at all. Thus, when some very low molecular weight organic amines and acids are present at low concentrations on the surface, cyclodextrins do not effectively complex with them.

  The cavities in the cyclodextrin in the deodorizing composition of the present invention are essentially filled while in solution so that the cyclodextrin can absorb various odorous molecules when the solution is applied to the surface. Should be left intact (cyclodextrin remains uncomplexed). Underivatized (normal) β-cyclodextrin can be present at concentrations up to a solubility limit of about 1.85% (about 1.85 g in 100 g water) under conditions of use at room temperature.

Preferably, the cyclodextrins used in the present invention are α-cyclodextrins and / or their derivatives, γ-cyclodextrins and / or their derivatives, derivatized β-cyclodextrins, and / or mixtures thereof. As shown in FIG. Cyclodextrin derivatives mainly consist of molecules in which some OH groups are converted to OR groups. Cyclodextrin derivatives include, for example, those having a short chain alkyl group such as methylated cyclodextrins and ethylated cyclodextrins where R is a methyl group or an ethyl group; R is —CH ₂ —CH (OH) — CH ₃ or ^- CH ₂ CH ₂ -OH hydroxypropyl cyclodextrins are groups and / or those having a hydroxyalkyl substituents such as hydroxyethyl cyclodextrins; branched cyclodextrin such as maltose binding cyclodextrins s; R is a cation such as those containing 2-hydroxy-3- (dimethylamino) propyl ether is low is cationic at _{pH CH 2 -CH (OH) -CH} 2 -N (CH 3) 2 sex cyclodextrins; quaternary ammonium, eg, R is CH ₂ -C ^{_{(OH) -CH 2 -N + (}} CH 3) 3 Cl - in which 2-hydroxy-3- (trimethylammonio) propyl ether chloride groups, carboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinyl rate Anionic cyclodextrins such as carboxymethyl / amphoteric cyclodextrins such as carboxymethyl / quaternary ammonium cyclodextrins; cyclodextrins in which at least one glucopyranose unit has a 3-6-anhydro-cyclomalto structure, for example Mono-3-6-anhydrocyclodextrin, “Optimal Performances with Minimal Chemical Modification of Cyclodextrins” (F. Diedaini-Pilard and B .Pali (Perly), The 7th International Cyclodextrin Symposium Abstracts, April 1994, page 49, and mixtures thereof, including other cyclodextrin derivatives. U.S. Pat. No. 3,426,011 (issued Feb. 4, 1969); 3,453,257; 3,453,258; 3,453, No. 259; and No. 3,453,260 (all Permata et al., All issued July 1, 1969); No. 3,459,731 (Gramera et al., Issued August 5, 1969) No. 3,553,191 (Palmata et al., Issued on January 5, 1971); No. 3,565,887 (Palmata et al., Issued on February 23, 1971); No. 152 (Szejtli et al., Issued August 13, 1985); No. 4,616,008 (Hirai et al., Issued October 7, 1986); No. 4,678,598 (Ogino et al., Issued July 7, 1987); 4,638,058 (Brandt et al., Issued January 20, 1987); and 4,746,734. (Tsuchiyama et al., Issued May 24, 1988). Additional cyclodextrin derivatives suitable herein are V.D. T.A. D'Souza and K.S. B. Lipkowitz, chemical review: cyclodextrins (CHEMICAL REVIEWS: CYLCODEXTRINS), Vol. 98, No. 5 (American Chemical Society, July / August, 1998).

  Very water-soluble cyclodextrins are those having a water solubility of at least about 10 g in 100 mL water at room temperature, preferably at least about 20 g in 100 mL water, more preferably at least about 25 g in 100 mL water at room temperature. The availability of solubilized uncomplexed cyclodextrins is essential for effective and efficient odor control performance. The solubilized water-soluble cyclodextrin can exhibit more efficient odor control performance than a water-insoluble cyclodextrin when attached to a surface, particularly a carpet surface.

  Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein include hydroxypropyl α-cyclodextrin, methylated α-cyclodextrin, methylated β-cyclodextrin, hydroxyethyl β-cyclodextrin, and hydroxypropyl β-cyclodextrin. The hydroxyalkyl cyclodextrin derivative preferably has a degree of substitution of about 1 to about 14, more preferably about 1.5 to about 7, wherein the total number of OR groups per cyclodextrin is expressed as the degree of substitution. Defined. Methylated cyclodextrin derivatives typically have a degree of substitution of about 1 to about 18, preferably about 3 to about 16. A known methylated β-cyclodextrin is heptakis-2,6-di-O-methyl-β-cyclodextrin, commonly known as DIMEB, in which each glucose unit contains about 2 methyl groups. And the degree of substitution is about 14. A more commercially available, preferred methylated β-cyclodextrin is a randomly methylated β-cyclodextrin with different degrees of substitution, usually about 12.6, commonly known as RAMEB. Yes. DIMEB has a greater effect on the surface activity of the preferred surfactant than RAMEB, so RAMEB is preferred over DIMEB. Preferred cyclodextrins are available, for example, from Cerestar USA, Inc. and Wacker Chemicals (USA), Inc.

  It is also preferred to use a mixture of cyclodextrins. Such a mixture absorbs odors more broadly by complexing with a wider range of odoriferous molecules having a wider range of molecular sizes. Preferably, at least a portion of the cyclodextrin is α-cyclodextrin and derivatives thereof, γ-cyclodextrin and derivatives thereof, and / or derivatized β-cyclodextrin, more preferably α-cyclodextrin or α A mixture of a cyclodextrin derivative and a derivatized β-cyclodextrin, still more preferably a mixture of a derivatized α-cyclodextrin and a derivatized β-cyclodextrin, most preferably , A mixture of hydroxypropyl α-cyclodextrin and hydroxypropyl β-cyclodextrin, and / or a mixture of methylated α-cyclodextrin and methylated β-cyclodextrin.

  Since cyclodextrins can be the optimal breeding ground for certain microorganisms, especially when in aqueous compositions, it is preferred to include a water-soluble preservative as described below, which is the growth of microorganisms. Is effective in increasing the storage stability of aqueous odor absorbing solutions containing water-soluble cyclodextrins.

(Odor blocking agent)
The “odor blocking agent” can be used as an arbitrary odor suppressing agent for reducing the influence of bad odor. In order to be effective, odor blockers usually must always be present. If the odor blocking agent evaporates before the odor source disappears, the odor is not significantly suppressed. Odor blocking agents may also tend to adversely affect aesthetics by blocking desirable odors such as perfumes.

  Non-limiting examples of odor blockers suitable as odor inhibitors for the composition include 4-cyclohexyl-4-methyl-2-pentanone, 4-ethylcyclohexyl methyl ketone, 4-isopropylcyclohexyl methyl ketone, cyclohexyl methyl ketone, 3-methylcyclohexyl methyl ketone, 4-tert. -Butylcyclohexyl methyl ketone, 2-methyl-4-tert. Butyl cyclohexyl methyl ketone, 2-methyl-5-isopropyl cyclohexyl methyl ketone, 4-methyl cyclohexyl isopropyl ketone, 4-methyl cyclohexyl sec. Butyl ketone, 4-methylcyclohexyl isobutyl ketone, 2,4-dimethylcyclohexyl methyl ketone, 2,3-dimethylcyclohexyl methyl ketone, 2,2-dimethylcyclohexyl methyl ketone, 3,3-dimethylcyclohexyl methyl ketone, 4,4-dimethyl Cyclohexyl methyl ketone, 3,3,5-trimethylcyclohexyl methyl ketone, 2,2,6-trimethylcyclohexyl methyl ketone, 1-cyclohexyl-1-ethyl formate, 1-cyclohexyl-1-ethyl acetate, 1-cyclohexyl-1 Ethyl propionate, 1-cyclohexyl-1-ethyl isobutyrate, 1-cyclohexyl-1-ethyl n-butyrate, 1-cyclohexyl-1-propyl acetate, 1-cyclohexyl-1-propyl Pyr n-butyrate, 1-cyclohexyl-2-methyl-1-propyl acetate, 2-cyclohexyl-2-propyl acetate, 2-cyclohexyl-2-propylpropionate, 2-cyclohexyl-2-propylisobutyrate, 2 -Cyclohexyl-2-propyl n-butyrate, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), 2,2-dimethyl-1,3-dioxane-4,6-dione (meldrum acid), spiro- [4.5] -6,10-dioxa-7,9-dioxodecane, spiro- [5.5] -1,5-dioxa-2,4-dioxoundecane, 2,2-hydroxymethyl-1,3 -Dioxane-4,6-dione and 1,3-cyclohexadione. Odor blocking agents are disclosed in U.S. Pat. Nos. 4,009,253; 4,187,251; 4,719,105; 5,441,727; and 5,861,371. Is disclosed in more detail in this issue.

(Reactive aldehydes)
As an optional odor suppressor, reactive aldehydes can be used as an odor suppressor in order to reduce the effects of malodor. Non-limiting examples of suitable reactive aldehydes include class I aldehydes, class II aldehydes, and mixtures thereof. Non-limiting examples of class I aldehydes include anisaldehyde, o-allylvanillin, benzaldehyde, cuminaldehyde, ethyl-obepine, ethyl vanillin, heliotropin, tolylaldehyde and vanillin. Non-limiting examples of class II aldehydes include 3- (4′-tert.butylphenyl) propanal, 2-methyl-3- (4′tert.butylphenyl) propanal, 2-methyl-3- (4 ′ -Isopropylphenyl) propanal, 2,2-dimethyl-3- (4-ethylphenyl) propanal, cinnamic aldehyde, α-amylcinnamic aldehyde and α-hexylcinnamic aldehyde. These reactive aldehydes are described in more detail in US Pat. No. 5,676,163.

  When used, the reactive aldehydes can include a combination of at least two aldehydes, one aldehyde being an acyclic aliphatic aldehyde, a non-terpene aliphatic aldehyde, a non-terpene alicyclic Selected from the formula aldehydes, terpene aldehydes, aliphatic aldehydes substituted with aromatic groups, and bifunctional aldehydes; the second aldehydes are insensitive to aldehyde functional groups attached to the aromatic ring. Aldehydes having saturated α and aldehydes in which the aldehyde group is on the aromatic ring are selected. This combination of at least two aldehydes is described in more detail in PCT International Patent Application Publication WO 00/49120.

  As used herein, the term “reactive aldehydes” refers to (i) a reaction product of an aldehyde and an alcohol, (ii) a reaction product of a ketone and an alcohol, or (iii) the same aldehyde as the aldehyde. Further included is a deodorizing material which is a reaction product of or with a different aldehyde. Such deodorizing substances include: (a) an acetal or hemiacetal produced by the reaction of an aldehyde and carbinol; (b) a ketal or hemiketal produced by the reaction of a ketone and carbinol; (c) a cyclic triacetal. Alternatively, it can be a mixed cyclic triacetal of at least two aldehydes, or a mixture of any of these acetals, hemiacetals, ketals, hemiketals or cyclic triacetals. These deodorant perfume materials are described in more detail in PCT International Patent Application Publication No. WO 01/07095.

(Flavanoids)
Flavanoids can also be used as odor inhibitors. Flavanoids are compounds based on the C ₆ · C ₃ · C ₆ flavan skeleton. Flavanoids can be found in typical essential oils. Such oils include essential oils extracted by dry distillation from coniferous and flowering plants such as cedar, Japanese cypress, eucalyptus, Japanese red pine, dandelion, kumazasa and aquatic grass, including α-pinene, β-pinene, myrcene. Terpene-based materials such as Fencon and Kamfen. Moreover, the extract from tea leaves is also mentioned. A description of such substances can be found in JP02284997 and JP040308855 (metal salts)
The odor suppressor of the present invention can contain a metal salt for the effect of suppressing malodor. The metal salts are selected from the group consisting of copper salts, zinc salts and mixtures thereof.

  Preferred zinc salts have malodor control ability. As disclosed in U.S. Pat. Nos. 4,325,939 and 4,469,674, zinc is most frequently used for its ability to ameliorate malodors, such as gargle products. It is used for. Highly ionized and soluble zinc salts such as zinc chloride provide the best source of zinc ions. Preferred zinc salts are selected from the group consisting of zinc borate, zinc caprylate, zinc chloride, zinc ricinoleate, zinc sulfate heptahydrate, zinc undecylenate and mixtures thereof.

Preferably the metal salts are water-soluble zinc salt, a copper salt, or a mixture thereof, more preferably zinc salts, especially ZnCl _2. These salts are preferably present in the present invention as odor inhibitors to absorb primarily amine and sulfur containing compounds. Low molecular weight sulfur-containing materials such as sulfides and mercaptans are constituents of many types of malodors such as food odor (garlic, onion), body / sweat odor, halitosis and the like. Low molecular weight amines are also components of many malodours, such as food odor, body odor, urine and the like.

When used, the zinc salt can be combined with an anionic surfactant having the formula R— (O—CH ₂ —CH ₂ ) _x —O—CH ₂ COO ^— , where R is aliphatic An alcohol substituent or an alkylaryl substituent, and X is at least 2. Such an anionic surfactant can act as a controlled release agent of the zinc salt to improve the malodor control properties of the composition. This combination of zinc salt and anionic surfactant is described in more detail in US Pat. No. 6,358,469.

  When used, zinc salts can also be combined with carbonates and / or bicarbonates to improve the malodor control properties of the composition. When the zinc salt is combined with carbonate and / or bicarbonate, the composition preferably has a phosphate with more than one-(P = O)-group and more than one acid functionality. Further comprising a stabilizing anion selected from organic acids. This zinc salt, carbonate and / or bicarbonate combination, and stabilizing anion are described in more detail in US Pat. No. 6,015,547.

  Copper salts have some odor control capability. U.S. Pat. No. 3,172,817 (Leupold) disclosing a deodorizing composition for treating disposable articles containing at least a slightly water-soluble salt of acylacetone, including copper and zinc salts Et al.).

  When metal salts are added to the compositions of the present invention as odor inhibitors, they are typically from about 0.001 weight of the composition to an effective amount that provides a saturated salt solution, preferably about 0.002. It is present at a concentration of from wt% to about 25 wt%, more preferably from about 0.003 wt% to about 8 wt%, even more preferably from about 0.1 wt% to about 5 wt%.

(Zeolites)
The odor suppressor herein can also be zeolites. A preferred class of zeolites is characterized as "intermediate" silicate / aluminate zeolites. Intermediate zeolites are characterized by a SiO ₂ / AlO ₂ molar ratio of less than about 10. Preferably, the SiO ₂ / AlO ₂ molar ratio ranges from about 2 to about 10. This intermediate zeolite may be advantageous over "high" zeolites. These intermediate zeolites have a higher affinity for amine-type odors, have a larger surface area, are therefore more weight efficient in absorbing odors, and are more moisture resistant than high zeolites, Maintain more odor absorption capacity in water. A wide variety of intermediate zeolites suitable for use herein include Valfor® CP 301-68, Valfor® 300-63, available from PQ Corporation, It is commercially available as Valfor® CP300-35 and Valfo® CP300-56 and from Conteka as the CBV100® series of zeolites.

  Also preferred are zeolitic materials marketed under the trade names Abscents® and Smellrite®, available from Union Carbide Corporation and UOP. Such materials are preferred over intermediate zeolites for the control of sulfur containing odors such as thiols and mercaptans.

  When zeolites are used as odor control agents in compositions that are sprayed onto the surface, the zeolitic material preferably has a particle size of less than about 10 microns and the composition at a concentration of less than about 1% by weight of the composition. Present in.

(Activated carbon)
Activated carbon is another odor control agent suitable for incorporation into the present composition. Carbon materials suitable for use in the present invention are materials well known in commercial practice as absorbents for organic molecules and / or for air cleaning purposes. Often, such carbon materials are referred to as “activated” carbon or “activated” charcoal. Such carbons are Calgon-Type CPG®; Type PCB®; Type SGL®; Type CAL®; and Type OL®. ) From commercial sources.

  When activated carbon is used as an odor control agent in a composition sprayed on the surface, the activated carbon preferably has a particle size of less than about 10 microns and is present in the composition at a concentration of less than about 1% by weight of the composition. Exists.

  For purposes of this specification, any substance described herein as an odor control agent may be classified as another component described herein, Substances are classified as odor control agents.

(solvent)
The composition can further comprise an optional solvent. The solvent can serve to provide a composition that dries more quickly after being applied to the surface as compared to a composition that does not contain a solvent. If a composition that dries quickly after application to the surface is desired, the composition preferably further comprises a solvent. Suitable solvents herein include monohydric and polyhydric alcohols. Monohydric alcohols useful as solvents in the present composition include ethanol, n-propanol, isopropanol, mixtures thereof, and the like. Polyhydric alcohols useful as a solvent in the present composition include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycols such as glycerin, and mixtures thereof. Other suitable solvents include water miscible ethers, water miscible glycol ethers, and propylene glycol monomethyl ether acetate. Non-limiting examples of water miscible ethers include diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether and mixtures thereof. Non-limiting examples of water-miscible glycol ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether and These mixtures are mentioned.

  When present, the concentration of solvent in the composition is generally from about 0.1% to about 99.9%, preferably from about 0.5% to about 99%, more preferably from about 1% to about 90%. It is. When the composition is a spray composition (especially a non-aerosol), the concentration of alcohol is preferably less than about 35%, more preferably less than about 20%, even more preferably less than about 10% by weight of the composition. is there.

(Aerosol propellant)
Where the composition is in the form of an aerosol spray composition, the composition further comprises an aerosol propellant. Non-limiting examples of aerosol propellants suitable for the aerosol compositions herein include aliphatic hydrocarbons such as butane, isobutane and propane; low molecular weight halogenated hydrocarbons such as chlorodifluoromethane (preferably Chlorinated and / or fluorinated hydrocarbons); soluble gases such as carbon dioxide; nitrogen gas; compressed air; other materials well known in the art.

When present, the aerosol propellant is typically incorporated into the composition at a concentration of from about 2% to about 60%, preferably from about 3% to about 50% by weight of the composition.
Particularly suitable aerosol propellants for incorporation into the composition are described in detail in US Pat. No. 4,520,142.

(Surfactant)
In order to improve the ability of the composition to “wet” the surface to be treated (ie to improve the ability of the composition to spread across the surface), the composition preferably further comprises an optional surfactant. . Preferably, the composition is from about 0.001% to about 90%, preferably from about 0.01% to about 80%, more preferably from about 0.05% to about 70% by weight of the composition. Surfactant or a mixture of surfactants at a concentration of Where the composition is intended to be sprayed onto a surface via a spray dispenser, the composition is preferably less than about 5%, preferably less than about 3%, more preferably about 1% by weight of the composition. Include any surfactant at a concentration of less than%.

Surfactants are generally well known in the detergent art. Suitable surfactants for the compositions of the present invention include anionic, nonionic, cationic, amphoteric, bipolar and mixtures of the above types.
Preferred surfactants are described in detail in US Patent Application Publication US2002 / 0011584A1.

(Anionic surfactant)
Anionic surfactants can be optionally incorporated into the composition. Many suitable non-limiting examples of the class of anionic surfactants include Surfactants and Interfacial Phenomena, 2nd edition, Milton J. et al. Rosen (Milton J. Rosen, 1989, John Wiley & Sons, Inc.), pages 7-16. Non-limiting examples of additional suitable anionic surfactants are described in “Handbook of Surfactants”, M.M. R. MRPorter, 1991, Blackie & Son Ltd, pages 54-115, and references thereof.

Structurally, suitable anionic surfactants contain at least one hydrophobic moiety and at least one hydrophilic moiety. The surfactant may contain a plurality of hydrophobic moieties and / or a plurality of hydrophilic moieties, but preferably contains no more than about 2 hydrophobic moieties and no more than about 3 hydrophilic moieties. The hydrophobic moiety is typically composed of either hydrocarbon as an alkyl group or as an alkylaryl group. The alkyl group typically contains from about 6 to about 22 carbons, preferably from about 10 to about 18 carbons, more preferably from about 12 to about 16 carbons; Typically, it contains an alkyl group containing from about 4 to about 6 carbons. Each alkyl group can be branched or straight chain and is either saturated or unsaturated. A typical aryl group is benzene. Some of the typical hydrophilic groups for anionic surfactants include —CO ₂ ⁻ , —OSO ₃ ⁻ , —SO ₃ ⁻ , — (OR ₁ ) _x —CO ₂ ⁻ , — (OR _{1 ^{) x -OSO 3 -, - (}} OR 1) x -SO 3 - although include, but are not limited to, wherein, x is less than about 10, preferably less than about 5. Some non-limiting examples of suitable surfactants include Stepanol (R) WAC, Biosoft (R) 40 (Stepan Co., Northfield, Illinois). )).

  Anionic surfactants can also be produced by sulphating or sulphonating animal or vegetable oils. Examples of this type of surfactant include sulfated canola available from Freedom Chemical Co. (Charlotte, NC), owned by BF Goodrich. Oil and sulfated castor oil (Freedom SCO-75).

Non-limiting examples of suitable anionic surfactants include C ₈ -C ₂₂ alkyl fatty acid salts; C ₁₀ -C ₁₄ alkyl benzene sulfonates; C ₁₀ -C ₂₂ alkene sulfonates; C ₁₀ -C ₂₂ alkyl ether sulfonates; C ₁₀ -C ₂₂ alkyl sulfate; C ₄ -C ₁₀ dialkyl sulfosuccinate; C ₁₀ -C ₂₂ acyl methionate; alkyl diphenyl oxide sulfonate; alkyl naphthalene sulfonate; 2-acetamide hexadecane sulfonate; alkyl glyceryl ether sulfonate; N-alkyl substituted succinates are mentioned. Anionic surfactants which are water-soluble alkylbenzene sulfonate salts of organic sulfur reaction products are described in US Pat. Nos. 2,220,099 and 2,477,383. Of particular value are linear linear alkyl benzene sulfonates having an average alkyl group of about 11 to 13 alkyl groups, abbreviated as C _{11 to} C ₁₃ LAS. Other anionic surfactants are described in US Pat. No. 6,358,469, which is preferred when the composition includes a zinc salt in combination with a carbonate and / or bicarbonate.

  When the composition includes uncomplexed cyclodextrin as an odor control agent, the anionic surfactant is preferably cyclodextrin compatible, which does not tend to form a complex with the cyclodextrin. Means that. A non-limiting example of a cyclodextrin compatible anionic surfactant is an alkyl diphenyl oxide disulfonate having the general formula:

式中、Ｒはアルキル基である。この種類の界面活性剤の例は、商標名ダウファックス（Dowfax）（登録商標）でダウ・ケミカル社（Dow Chemical Company）から入手でき、ここでＲは直鎖又は分枝状Ｃ₆〜Ｃ₁₆アルキル基である。これらのシクロデキストリン適合性アニオン性界面活性剤の例は、ダウファックス（Dowfax）３Ｂ２であり、Ｒはほぼ直鎖Ｃ₁₀基である。

In the formula, R is an alkyl group. An example of this type of surfactant is available from Dow Chemical Company under the trade name Dowfax®, where R is linear or branched C ₆ -C _16. It is an alkyl group. An example of these cyclodextrin compatible anionic surfactants is Dowfax 3B2, where R is an approximately linear C ₁₀ group.

(Nonionic surfactant)
The composition can optionally include a nonionic surfactant, which is a preferred surfactant in the composition. Non-limiting examples of suitable nonionic surfactants include alkyl ethoxylated surfactants, block copolymer surfactants, castor oil surfactants, sorbitan ester surfactants, polyethoxylated fatty alcohol surfactants, Examples include glycerol mono fatty acid ester surfactants, polyethylene glycol fatty acid ester surfactants, and mixtures thereof. These nonionic surfactants are described in more detail in US Patent Application Publication US2002 / 0011584A1.

  Alkyl ethoxylated surfactants and castor oil surfactants are preferred nonionic surfactants. Castor oil surfactants include polyoxyethylene castor oil ether or polyoxyethylene hydrogenated castor oil ether, which are partially or fully hydrogenated. Preferred hydrogenated castor oil surfactants are commercially available from Nikko under the trade names HCO40 and HCO60 and from BASF under the trade names Cremphor ™ RH40, RH60 and CO60.

(Cationic surfactant)
Cationic surfactants can also be incorporated into the composition. When used in aqueous compositions that are sprayed onto fabrics, cationic surfactants can improve the ability of the composition to penetrate between fabric fibers, which reduces malodor and / or reduces the wrinkle appearance of the fabric. In that respect, better performance can be provided. Cationic surfactants can also be useful in softening fabrics treated with the present compositions.

  Suitable cationic surfactants include a wide variety of quaternary compounds. A preferred cationic surfactant is a diester quaternary ammonium compound (“DEQA”). These and other preferred quaternary compounds are described in detail in US Patent Application Publication US2002 / 0011584A1.

  If the cationic surfactant acts as either an antimicrobial active or a preservative, it is classified for the purposes of the present invention as an antimicrobial active / preservative as described below.

(Amphoteric surfactant)
Amphoteric surfactants can also be used in the composition. Amphoteric surfactants, also called ampholytic surfactants, are widely used as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines. The aliphatic radical can be straight or branched, one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, at least one of which is Contains anionic water-soluble groups such as carboxy, sulfate or sulfonate. Examples of suitable amphoteric surfactants can be found in US Pat. No. 3,929,678 at column 19, lines 18-35.

(Bipolar surfactant)
The composition can optionally include a bipolar surfactant. Dipolar surfactants are derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. As may be widely described.

(Free perfume)
The stable aqueous composition of the present invention preferably contains a free fragrance as an optional ingredient. As used herein, the term “free perfume” means a perfume that is in the composition but not contained within the microcapsules. Free perfume is desirable for the composition to provide a refreshing impression on the surface treated with the stable aqueous composition of the present invention. Free perfume is particularly desirable for compositions treating fabrics because it is important to give a fresh impression to fabrics, especially clothing. Free perfume may be desirable to provide a quick “burst” of perfume scent when the composition is applied to a surface, for example by spraying the composition onto a fabric, decorative surface, or carpet.

  Perfume materials suitable for incorporation into the present compositions include, for example, US Pat. No. 5,939,060 (Trinh et al., Issued August 17, 1999), column 2, line 38 to column 7, 53. Disclosed on the line.

  If free perfume is included in the stable aqueous composition of the present invention, it can be included in a wide variety of concentrations. The free perfume is typically about 0.0001% to about 10%, preferably about 0.001% to about 7%, more preferably about 0.01% to about 5% by weight of the composition. Concentration in weight percent.

(Antimicrobial active substance / preservative)
The composition can further comprise an antimicrobial active / preservative if desired. As discussed above, the antimicrobial active substance can constitute the active substance contained in the microcapsules of the present composition. Additionally or alternatively, the composition can include free antimicrobial active / preservative, meaning an antimicrobial active / preservative that is not contained within the microcapsules of the composition.

  Suitable antimicrobial actives / preservatives for incorporation into the composition include many quaternary compounds, biguanide compounds, and other antimicrobial actives having antimicrobial activity. These substances are effective in inhibiting the growth of microorganisms in the composition itself (ie acting as preservatives) and / or killing the surface microorganisms treated with the composition (ie acting as antibacterial active substances) Can be incorporated into the composition in an amount.

Suitable antimicrobial actives / preservatives herein include quaternary compounds, biguanide compounds, and mixtures thereof. Non-limiting examples of quaternary compounds include the commercially available Barquat (R) (available from Lonza), Maquat (R) (available from Mason) ), Benzalkonium chlorides such as Variquat® (available from Witco / Sherex), and Hyamine® (available from Lonza) and / or or substituted benzalkonium chloride like; Lonza of Badakku (Bardac) (R) di (C ₆ -C ₁₄₎ such as the product alkyl di short chain (C ₁ ~ ₄ alkyl and / or hydroxyalkyl (Hydroxyalkl)) fourth N- (3-chloroallyl) hexaniumium, such as Dowicide (R) and Dowicil (R), available from Dow Loride; Benzethonium chloride such as Hyamine® from Rohm &Haas; Hyamine® supplied by Rohm & Haas Methyl benzethonium chloride represented by 10X, cetylpyridinium chloride such as Cepacol chloride available from Merrell Labs; and diester quaternary ammonium compounds. Examples of preferred dialkyl quaternary compounds are di (C ₈ ) such as didecyldimethylammonium chloride (Bardac® 22) and dioctyldimethylammonium chloride (Bardac® 2050). -C ₁₂₎ dialkyl dimethyl ammonium chloride. The quaternary compounds useful as cationic preservatives and / or antimicrobial agents herein preferably comprise dialkyldimethylammonium chlorides, alkyldimethylbenzylammonium chlorides, dialkylmethylbenzylammonium chlorides and mixtures thereof. Selected from the group. Another preferred cationic antimicrobial active useful herein is diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride (commercially available from Rohm & Haas under the trade name Hyamine® 1622). And (methyl) diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride (ie methylbenzethonium chloride).

  Non-limiting examples of biguanide compounds include 1,1'-hexamethylenebis (5- (p-chlorophenyl) biguanide), commonly known as chlorhexidine, and poly (hexamethylenebiguanide) hydrochloride, Cosmoci ) (Registered trademark) CQ (registered trademark), Vantocil (registered trademark) IB. Other useful antimicrobial active substances include bis-biguanide alkanes. The water-soluble salts that can be used are chlorides, bromides, sulfates, alkyl sulfonates such as methyl sulfonate and ethyl sulfonate, phenyl sulfonates such as p-methylphenyl sulfonate, nitrate, acetate. Gluconate, etc.

  Non-limiting examples of other suitable antimicrobial actives include pyrithione (especially zinc complex (ZPT)), Octopirox®, dimethyldimethylol hydantoin (Glydant®), Sodium sulfite, sodium hydrogen sulfite, imidazolidinyl urea (Germall 115®), diazolidinyl urea (Gamal II®), benzyl alcohol, 2-bromo-2-nitropropane-1,3-diol ( Bronopol (registered trademark), formalin (formaldehyde), iodopropenyl butyl carbamate (Polyphase P100 (registered trademark)), chloroacetamide, methanamine, methyldibromonitrile glutaronitrile (1,2-dibromo- 2,4-dicyanobuta Or Tektamer®), glutaraldehyde, 5-bromo-5-nitro-1,3-dioxane (Bronidox®), phenethyl alcohol, o-phenylphenol / sodium o- Phenylphenol, sodium hydroxymethyl glycinate (Suttocide A®), polymethoxybicyclic oxazolidine (Nuosept C®), dimethoxan, Thimersal, dichlorobenzyl alcohol, captan, Chlorphenenesin, dichlorophene, chlorbutanol, glyceryl laurate, halogenated diphenyl ether, 2,4,4′-trichloro-2′-hydroxy-diphenyl ether (Triclosa n) (registered trademark) or TCS), 2,2′-dihydroxy-5,5′dibromo-diphenyl ether, phenolic compounds (described in US Pat. No. 6,190,674), para-chloro-meta-xylenol ( PCMX), chlorothymol, phenoxyethanol, phenoxyisopropanol, 5-chloro-2-hydroxydiphenylmethane, resorcinol and its derivatives (described in US Pat. No. 6,190,674), 5-chloro2,4-dihydroxydiphenylmethane, 4 ′ -Chloro 2,4-dihydroxydiphenylmethane, 5-bromo 2,4-dihydroxydiphenylmethane, 4'-bromo 2,4-dihydroxydiphenylmethane, bisphenolic compounds (described in US Pat. No. 6,190,674), parabens ( US Pat. No. 6,19 0,674), halogenated carboanilides (described in US Pat. No. 6,190,674), and mixtures thereof.

  When present in the composition of the present invention, the antimicrobial active is included in an effective amount to kill surface microorganisms treated with the composition, typically from about 0.001% to about 20% by weight of the composition. %, Preferably about 0.01% to about 10% by weight, more preferably about 0.05% to about 5% by weight.

(Wrinkle inhibitor)
The composition can optionally further comprise a wrinkle suppressant, which helps to prevent and / or suppress the formation of wrinkles on the surface treated with the composition, particularly the fabric. Wrinkle inhibitors useful herein include fiber lubricants, shape-retaining polymers, hydrophilic plasticizers, lithium salts, and mixtures thereof. Such wrinkle suppressors are described in detail in US Pat. No. 6,001,343 (Trinh et al., Issued Dec. 14, 1999). A wrinkle-suppressing composition that may be suitable as a base composition of the present invention comprising microcapsules containing an active substance, particularly as a composition that can be used in a cabinet-type device or a bag-type device for conditioning clothing, is also a Pending US patent application Ser. No. 09 / 674,224 (Hubesch et al., Filed Apr. 27, 1998 (related to PCT International Publication No. WO 99/55950, published Nov. 4, 1999)); and simultaneously Disclosed in pending US patent application Ser. No. 09 / 673,600 (Woo et al., Filed Apr. 27, 1998 (PCT International Publication No. WO 99/55816 (published Nov. 4, 1999)). Yes.
Other additional optional ingredients may be included in the composition. Non-limiting examples of additional optional ingredients include brighteners, colorants and the like.

  The composition typically has a pH of about 2 to about 10, preferably about 3.5 to about 9.5, more preferably about 4 to about 9. Depending on the materials included in the composition, it may be desirable to adjust the pH of the composition to acidic or alkaline. For example, if the composition contains an acid activated dispersant (eg, acrylate / aminoacrylate copolymers such as ALCOGUM® L-511), the composition is preferably less than about 8, preferably Has a pH of less than about 7.5, more preferably less than about 7. On the other hand, for example when the composition contains an alkali activated dispersant (eg, acrylate / acrylic polymers such as ALCOGUM® SL-70), the composition is preferably greater than about 4 Preferably having a pH greater than about 5, more preferably greater than about 5.5.

  The compositions of the present invention are aqueous liquids (eg, fabric refreshers such as those described in US Pat. No. 6,146,621), aerosols (as described in US Pat. No. 4,520,142). Such as those described in US Pat. No. 4,701,319, gels (eg, automatic dishwashing gels such as those described in US Pat. No. 5,384,061), pastes (eg, those described in US Pat. No. 4,701,319). Toothpastes), lotions (eg skin lotions such as those described in US Pat. No. 5,968,258), powder detergent granules (eg US Pat. No. 5,338,476). Laundry detergent compositions such as those), shampoo / conditioners (such as those described in US Pat. No. 6,221,817), bar soap (Such as those described in U.S. Pat. No. 5,254,281) can be in the form of such. The compositions also include softener dryer sheets (see, eg, US Pat. No. 4,808,086), premoist sheets for household dry cleaning processes (see, eg, US Pat. No. 5,630,086). 848), premoist cleaning wipes (see, eg, US Pat. No. 6,183,763), dry waste cleaning sheets (see, eg, US Pat. No. 5,525,397) ); And diapers (see, eg, US Pat. No. 6,319,239). The composition can also be incorporated into a plug-in type air freshener (such as described in US Pat. No. 5,976,503). Preferably, the composition is an aqueous liquid, especially one that contains a relatively large amount of water.

  A preferred method of the invention relates to treating a surface, preferably a fabric, with a stable aqueous composition of the invention, comprising contacting the surface with the stable aqueous composition. As used herein, the term “fabric” is meant to encompass a variety of fabrics and articles composed of fabrics and / or fibers, such as clothing, curtains, drapes, decorative furniture, carpets, bed linens. , Bath linens, tablecloths, sleeping bags, tents, car interiors (for example, car carpets, cloth car seats) and the like. The method relates more particularly to reducing the odor of surfaces, especially fabrics, and / or reducing the wrinkle appearance of fabrics. The surface is preferably sprayed onto the surface with a dilute aqueous composition of the present invention via a spray dispenser, or the concentrated composition of the present invention is added to, for example, a typical laundry process wash and / or rinse cycle. It is processed by either.

Preferred methods herein include a method of reducing malodor on a surface with a odor sensation (preferably a fabric), the method comprising contacting the surface with a stable aqueous composition as described above. .
The compositions for reducing malodour herein can be used by dispensing, for example, placing an aqueous solution in a dispensing means, preferably a spray dispenser, and spraying an effective amount on the desired surface or article. An effective amount as defined herein is an amount sufficient to absorb odors to the extent that it is not perceived by the human olfaction, but the item or surface is submerged with liquid or a puddle. It means an amount that is not appreciably visible, and therefore has no visible deposit when it is dry. Dispensing can be accomplished by using a spray device, rollers, pads, etc. In odor control, an effective amount as defined herein means an amount sufficient to absorb odor, preferably to the extent that it cannot be recognized by human olfaction, in order to bring about a noticeable reduction in the sensed odor. To do.

  The present invention includes a method of spraying an effective amount of the composition to reduce malodours on the surface of household items. Preferably, the household surface is selected from the group consisting of a countertop, cabinet, wall, floor, bathroom surface and kitchen surface.

  Additional methods include, for example, adding an aqueous liquid composition to a steam iron and then using the steam iron for fabric ironing. Another method includes adding the aqueous liquid composition to an apparatus for refreshing the fabric (as described in PCT International Publication No. WO 02/14594).

  Where the composition includes a wrinkle inhibitor, a method of suppressing fabric wrinkles is encompassed by the present invention, as described in detail in co-pending US Patent Application Publication US2002 / 0011584A1.

  The compositions of the present invention can be packaged in a wide variety of packages well known in the art. When the composition is an aqueous liquid composition, the composition is preferably packaged in a spray dispenser. Suitable spray dispensers can be operated manually or non-manually (eg, battery powered dispensers). A suitable spray dispenser is described in detail in US Pat. No. 6,284,231. When aerosol compositions are made, they are typically packaged in aerosol spray dispensers such as those described in US Pat. Nos. 3,436,772 and 3,600,325. Other suitable spray dispensers are: U.S. Pat. Nos. 4,082,223; 4,161,288; 4,434,917; 4,819,835; No. 303,867.

  The compositions of the present invention can be delivered in such a way as to generate foam. The foam of the present invention includes any dispersion of gas in a liquid. Foaming surfactants are typically used to promote foaming. These foaming surfactants preferably include higher alkyl benzene sulfonates in which the alkyl is linear; N-higher acyl sarcosides; α-olefin sulfonates; paraffin sulfonates; higher aliphatic acyl taurides and isethionates; Sulfates and sulfonates; including, but not limited to, tallow alcohol sulfate, sodium coconut oil monoglyceride sulfate and n-dodecylbenzene sulfonate as sodium, potassium and triethanolamine salts, among others. Usually, the anionic surfactant has a substantially balanced hydrophilic-lipophilic ratio and the higher alkyl or acyl is of 10-20 carbon atoms, preferably 12-18 carbon atoms. Exemplary methods of forming foam compositions are outlined in US Pat. No. 6,482,783 (Lewis et al.).

  The stable aqueous compositions (especially concentrated compositions) herein can also be packaged in bottles, particularly bottles with a measuring closure. The metering cap provides a convenient means of dispensing an appropriate amount of the composition, particularly when dispensing the concentrated composition into a cleaning and / or rinsing solution containing fabric that is processed in a typical laundry process. To do. The bottle also preferably includes a drain-back spout that allows the composition to be dispensed more easily and with less fouling. Non-limiting examples of suitable bottles are US Pat. No. 4,666,065 (Ohren, issued May 19, 1987); US Pat. No. 4,696,416 (Muckenfuhs et al., 1987). Issued September 29, 1991)); and U.S. Pat. No. 4,981,239 (Cappel et al., Issued January 1, 1991).

  The composition is made by mixing together the components that make up the composition. A preferred method of making the composition of the present invention is described in Example XV below.

  The following are non-limiting examples of the present invention.

上の実施例１〜８の各組成物において、それぞれの組成物のｐＨは、必要に応じて水酸化ナトリウム又は塩酸を用いて３〜１１に調整される。上の実施例１〜８のそれぞれのマイクロカプセルは、マイクロカプセルの総量の約０．００１重量％〜約９９．９重量％の、香料、着香料、殺真菌剤、光沢剤、静電気防止剤、しわ抑制剤、柔軟仕上げ剤、硬質表面洗浄剤、スキン及び／又はヘアコンディショニング剤、抗菌活性物質、ＵＶ保護剤、昆虫忌避剤、動物／害虫忌避剤、難燃剤、臭気抑制剤並びにこれらの混合物から成る群から選択される活性物質を含有する。

In each of the compositions of Examples 1-8 above, the pH of each composition is adjusted to 3-11 using sodium hydroxide or hydrochloric acid as needed. Each of the microcapsules of Examples 1-8 above is about 0.001% to about 99.9% by weight of the total amount of microcapsules perfume, flavoring agent, fungicide, brightener, antistatic agent, From wrinkle suppressants, softeners, hard surface cleaners, skin and / or hair conditioning agents, antibacterial actives, UV protection agents, insect repellents, animal / pest repellents, flame retardants, odor control agents and mixtures thereof Containing an active substance selected from the group consisting of:

Example 9
A 1 kg batch of the composition of Example 1 is made as follows. A mixer is used to blend the components of the composition in a 4 liter beaker. The mixer has a pitch blade of 10.16 cm (4 ″) and the mixing speed of the mixer is set to 26 rad / sec (250 RPM). The following ingredients are added sequentially to a 4 liter beaker: 834. 78 g water; 32.50 g ethanol; 1.00 g Silwet® L-7600; 0.50 g free perfume; 1.50 g 50% by weight perfume and 50% by weight myristin. As well as 1.89 g of polyacrylic acid, these ingredients are mixed for 5 minutes, and then 27.50 g of hydroxypropyl β-cyclodextrin is added to the beaker. A premix containing water and gellan gum is produced in a beaker. The mixer is a 2.54 cm (1 ″) pitch. Has a blade, mixing speed of the mixer is 104.7Rad / sec (1000 RPM). The following ingredients are added sequentially to a 400 milliliter beaker: 99.7 g water and 0.3 g gellan gum. The premix is heated to 75 ° C. and added to a larger batch to produce a 0.03% gellan gum composition. 0.33 g of Kathon (R) is added for storage. These ingredients are mixed for 10 minutes. The resulting composition has a pH of about 7.

  While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (10)

A composition for providing controlled release of an active substance comprising:
(A) a microcapsule containing the active substance and a stabilizer,
(B) a dispersant; and (c) a composition optionally comprising an aqueous carrier.   The microcapsules are urea formaldehydes, melamine formaldehydes, phenol formaldehydes, gelatin, poly (vinyl alcohol), poly (vinyl pyrrolidone), polyacrylates, polyamides, polyurethane, polymethacrylates, polyepoxides, cellulose acetate, Cellulose nitrate, cellulose acetate butyrate, ethyl cellulose polyester, polychlorotrifluoroethylene, ethyl acetate / vinyl acetate, saran, polystyrene, zein, paraffin wax, animal wax, vegetable wax, microcrystalline wax, polyethylene The composition of claim 1 comprising a material selected from the group consisting of waxes and mixtures thereof.   The active substance is a fragrance, a flavoring agent, a fungicide, a brightener, an antistatic agent, a wrinkle inhibitor, a softening agent, a hard surface cleaner, a skin and / or hair conditioning agent, an antibacterial active substance, a UV protective agent, A composition according to claim 1 or 2, selected from the group consisting of insect repellents, animal / pest repellents, flame retardants and mixtures thereof. The stabilizer is isopropyl myristate, diethyl phthalate, triethyl citrate, mineral oil, silicone oil, diethyl propyl acetate (acteate), benzyl phenyl acetate, citronellyl phenyl acetate, benzyl isoeugenol, diphenyl oxide, γ-dodecalactone, Dibutyl phthalate, methyl myristate, ethyl myristate, ethyl palmitate, benzyl salicylate, benzyl benzoate, pheyl ethyl phenyl acetate, geranyl phenyl acetate (aceate), benzyl cinnamate, ethylene brushate, ambretone ), Galaxolide, Tonalide, Exaltolide, Habanolide, Isoamyl Laurate, Cedryl Acetate, Hexyl Cinnaaldehyde, Pacho Realco Le, .delta. Guaien, .delta. cadinene, C ₁₀ or higher alcohols, Dowanol (Dowanol) (registered trademark), dipropylene myristate and tripropylene myristate, Isopar (R), orange terpenes and mixtures thereof 4. The composition according to any one of claims 1 to 3, which is selected from the group consisting of:   5. The composition of any one of claims 1-4, wherein the active agent and the stabilizer have a combined weight average Kobat number that is greater than about 1325.   The dispersant is pectin, alginate, arabinogalactan, carrageenan, gellan gum, xanthum gum, guar gum, acrylate / acrylic polymers, water-swellable clays, fumigated silicas, acrylate / aminoacrylate copolymers and their 6. A composition according to any one of the preceding claims, selected from the group consisting of a mixture.   The composition as described in any one of Claims 1-6 in which the said composition further contains the free fragrance | flavor which is not contained in the said microcapsule.   8. The composition of any one of claims 1 to 7, wherein the composition further comprises an effective amount of an antimicrobial active substance that kills microorganisms on the surface treated with the composition, wherein the antimicrobial active substance is not contained in the microcapsules. The composition according to item.   The composition according to any one of claims 1 to 8, wherein the composition further comprises an odor control agent.   10. A method for providing controlled release of an active substance on a surface comprising the step of contacting said surface with a composition according to any one of claims 1-9.